End capped polyalkylene carbonates

ABSTRACT

Polycarbonates, of the type formed by reacting an aliphatic or cycloaliphatic 1,2-monoepoxide with carbon dioxide and having substantially alternating units of epoxide and carbon dioxide, are improved in thermal stability by reacting the free hydroxyl groups thereon with a hydroxyl reactive phosphorus compound.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to polycarbonates having improved thermal stability and to a process for preparing such polycarbonates.

2. Description of the Prior Art

In recent years, there has been extreme interest expressed in a class of high molecular weight polycarbonates formed by reacting an aliphatic or cycloaliphatic epoxide with carbon dioxide. These high molecular weight polycarbonates are useful as molding compositions in the formation of fibers and articles. Typically, the polycarbonates are produced by reacting an epoxide, e.g. ethylene oxide, propylene oxide, isobutylene oxide with carbon dioxide under pressure in the presence of an organometallic catalyst. Amplification of this description of the process is shown in U.S. Pat. No. 3,585,168, U.S. Pat. No. 3,900,424 and U.S. Pat. No. 3,953,383. Variations in this basic process are reported in U.S. Pat. No. 3,706,713, U.S. Pat. No. 3,689,462 and U.S. Pat. No. 3,699,079.

Hydroxyl groups on low molecular weight liquid polycarbonates of the type formed by reacting aromatic polyhydric alcohol and phosgene or those obtained by reacting a dihydric alcohol and bischlorocarbonate have been capped with monomers to form solid polymers. Examples of capping agents include disubstituted acids for forming polyester-polycarbonates and isocyanates to form polyurethane-polycarbonates. Exemplary formulations are shown in U.S. Pat. Nos. 3,248,414; 2,999,844; 3,544,657; 3,897,391; and 3,689,462.

SUMMARY OF THE INVENTION

This invention relates to polycarbonates, particularly polyalkylene carbonates formed by reacting an epoxide and carbon dioxide, having improved thermal stability. The improved thermal stability of the polyalkylene carbonates is imparted by reacting the free hydroxyl groups on the polyalkylene carbonate with a hydroxyl reactive phosphorus compound of the type capable of forming an oxygen-phosphorous (O--P) bond. This reaction results in the formation of an oxygen-phosphorus bond which is more stable than the oxygen-hydrogen bond to depolymerization and thereby enhances thermal stability.

Accordingly, an aspect of this invention is to provide a normally solid polycarbonate with substantially alternating units of epoxide and carbon dioxide of improved thermal stability.

It is another aspect of the invention to form polycarbonates suited for producing molded products which are more resistant to thermal degradation than are molded products prepared from prior art polycarbonates.

It is a further aspect of the invention to provide polyalkylene carbonates that can be processed over a wider temperature range than was previously possible and to promote their life under normal use conditions.

It is still a further object to provide polyalkylene carbonates which can be utilized for the manufacture of films and packages and the in situ pasteurization of contents therein.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The polycarbonates suited for practicing this invention are normally solid at room temperature (70° F.) and atmospheric pressure and are represented by the formula: ##STR1## wherein: R₁ is a hydrogen atom, a halomethyl group, or a hydrocarbyl group having from 1 to 6 carbon atoms;

R₃ is hydrogen, a halomethyl group or a hydrocarbyl group having from 1 to 6 carbon atoms;

R₂ and R₄ are hydrogen, or a hydrocarbyl group having from 1 to 6 carbon atoms; or

R₁, r₂, r₃ and R₄ are combined together constituting a carbocyclic ring of from 4 to 7 carbon atoms;

The polycarbonates represented by the formula above are normally solid at room temperature (70° F.) and atmospheric pressure and contain alternating units of epoxide and carbon dioxide. These polycarbonates are formed by reacting an epoxide and carbon dioxide to form high molecular weight polycarbonates of from about 50,000 to 500,000, and preferably a molecular weight of from about 75,000 to 150,000. This converts to a plurality of repeating units (n) (as shown in a subsequent formula) of from about 250 to 6,500, and preferably from 500 to 1,500.

The epoxides suited for forming the polycarbonates generally are 1,2-epoxides which are conventionally used in forming polycarbonates represented by the formula above. The epoxides can be substituted with a plurality of organo groups represented by R₁, R₂, R₃ and R₄, as for example hydrocarbyl groups which, by definition, include lower alkyl, alkenyl, cycloaliphatic, aryl groups, and substituted groups, e.g. chlorine, alkyl, hydroxyl, ester and aldehyde groups. Typically, the groups pendant on the epoxide reactant are hydrogen, lower alkyl, e.g. methyl and ethyl, or phenyl groups. Examples of suitable epoxides include ethylene oxide, propylene oxide, styrene oxide, isobutylene oxide, 2,3 butylene oxide, epichlorohydrin, butylene oxide, diphenylethylene oxide, trimethylethylene oxide, cyclohexane epoxide, methyl cyclohexane epoxide, ethylene cyclohexane epoxide, and the like. Of these, ethylene and propylene oxide are preferred.

End capping of the normally solid polycarbonates of this invention is accomplished by reacting the polycarbonate with a hydroxyl reactive phosphorus compound under conditions effective for replacing the hydrogen atom and forming an oxygen-phosphorus bond. Any hydroxyl reactive phosphorus compound that is capable of (1) reacting with the active hydrogen atom for forming an oxygen-phosphorus bond with the polymer, and (2) does not effect substantial polymer degradation and degeneration under the reaction conditions, can be used in practicing this invention. Further, these hydroxyl reactive phosphorus compounds may be an organo-phosphorus compound and substituted with any group, e.g. nitro, halo, alkyl, sulfonyl, etc. so long as it does not result in polymer degradation.

Classes of hydroxyl reactive phosphorus compounds which can be used for end capping the hydroxyl groups on the polycarbonates of this invention include: organo halo phosphates, e.g. diphenyl chloro phosphate, dicyclohexyl bromo phosphate, dimethyl chloro phosphate, bis(4-nitrophenyl chloro phosphate and halo phosphines, e.g. chloro triphenyl phosphine, bis(chloro phenyl phosphino) ethane, chloro nitrophenyl phosphine, dichloroethyl phosphine and dicyclohexyl chloro phosphine, Px₃ + Px₅ where x is halogen, e.g. phosphorus trichloride, phosphorus pentachloride, phosphorous tribromide, dimethyl bromophosphine and diethyl bromo phosphine.

In end capping the free hydroxyl groups on the polycarbonate resins, the hydroxyl groups are contacted with the hydroxyl reactive phosphorus compound under conditions sufficient for effecting reaction and capping substantially all of the hydroxyl groups. Generally, because the polymer is a solid, it is preferable to end cap the polycarbonate by forming a dispersion of polycarbonate and hydroxyl reactive compound, by milling the polymer and hydroxyl reactive phosphorus compound or by extruding the compounds. In the first case, the polycarbonate is dispersed in an inert solvent or carrier such as tetrahydrofuran, chloroform, dioxane, benzene, acetone or methylene chloride, and the reaction carried out in that medium. In milling, considerable care must be exercised to insure that the temperature of the polycarbonate resin does not exceed the thermal degradation temperature.

In forming the end capped polycarbonate resin, sufficient hydroxyl reactive phosphorus compound is blended and contacted with the polycarbonate resin to react with substantially all of the free hydroxyl groups. To insure that substantially all of the hydroxyl groups are reacted, at least 20% of the stoichiometric excess of hydroxyl reactive compound is mixed with the polycarbonate.

After end capping, the polyalkylene carbonate polymer is more nearly represented by the formula: ##STR2## wherein R₁ is a halomethyl or a hydrogen, or a hydrocarbyl group having from 1 to 6 carbon atoms;

R₃ is hydrogen, a halomethyl group or a hydrocarbyl group having from 1 to 6 carbon atoms;

R₂ and R₄ are hydrogen or a hydrocarbyl group having from 1 to 6 carbon atoms; or

R₁, r₂, r₃ and R₄ are combined together constituting a carbocyclic ring of from 4 to 7 carbon atoms; and

n is a number from 250 to 6,500;

Z is the remainder of the phosphorus radical compound selected from the group consisting of phosphines, phosphates, phosphate and phosphonate.

In the above formula, Z by definition, is the remainder of a phosphorous compound group where the oxygen atom is bonded to a phosphorus atom and the valences pendant from that phosphorus atom are satisfied. The essential feature is to end cap the hydroxyl group with a phosphorus compound sufficiently reactive to form the oxygen-phosphorus bond as those groups pendant from that phosphorus atom can be any atoms sufficient to satisfy the valences on the phosphorus as represented by Z.

The following examples are provided to illustrate preferred embodiments of this invention, and are not intended to restrict the scope thereof. All temperatures are in degrees centigrade.

EXAMPLE I

A 7.5 gram sample of a polyethylene carbonate (PEC) formed by the procedure of Example 1 in U.S. Pat. No. 3,900,424 having alternating units of ethylene oxide and carbon dioxide, a molecular weight of 100,000 and a melting point of about 190°-200° C. was dissolved in 100 millileters chloroform. The polyethylene carbonate had free hydroxyl groups as evidenced by the presence of frequencies in the infrared spectrum at 3480 cm⁻¹ and 3640 cm⁻¹. The free hydroxyl groups assuming, 1.5 × 10⁻⁴ mols hydroxyl group in the polyethylene carbonate, were end capped by adding (0.05 mols) diphenyl chlorophosphate to the polyethylene carbonate solution and then stirring at ambient temperature (20°-25° C.) for about 40 hours. The reaction medium then was added slowly to methanol and a precipitate formed which was removed by filtration. Residual solvent in the precipitate was removed by placing the polymer in a vacuum. Infrared analysis of the resulting polymer showed that hydroxyl groups were reacted and capped with diphenyl phosphate units.

EXAMPLE 2

The procedure of Example 1 was followed except that chloro diphenyl phosphine was substituted for diphenyl chloro phosphate, thus providing a polyethylene carbonate end capped with phenyl urethane groups.

EXAMPLE 3

A 10g portion of polypropylene carbonate (PPC) having about 2 × 10⁻⁴ mols hydroxyl group, a molecular weight of approximately 100,000, a melting point of 180°-190° C. and alternating units of propylene oxide and carbon dioxide was dissolved in 100 ml of chloroform and 11.3 ml of pyridine. Then, 0.14 mols of diphenyl chloro phosphate were added over a one-half hour period to the polypropylene carbonate solution. After stirring for about two hours and maintaining a temperature of 25° C., the resulting mixture was washed with a 5% aqueous hydrochloric acid followed by washing with 5% aqueous sodium bicarbonate solution. The mixture was then slowly added to methanol and a precipitate resulted. Residual solvent was removed from the polymer by vacuum. Analysis of the product indicated that essentially all of the free hydroxyl groups were capped with phosphate groups.

EXAMPLE 4

Untreated polyethylene and polypropylene carbonate, i.e. those having terminal hydroxyl groups and end capped polyethylene and polypropylene carbonate resins, were evaluated for thermal stability by heating a 0.005 gram sample of the resin at a rate of 21/2°/min. from a temperature of 120° C. to the decomposition temperature as indicated by a weight loss of 5% based on the weight of the sample. The atmospheric environments used in the evaluation of the samples were air and nitrogen. The results of the evaluation are noted in Table 1.

                  TABLE 1                                                          ______________________________________                                                     Decomposition                                                                  Temperature ° C.                                                                     Decomposition                                                     Untreated Poly-                                                                             Temperature ° C. End                           Polycarbonate                                                                              Carbonate    Capped Polycarbonate                                  ______________________________________                                         Ex. 1 Air (PEC)                                                                            210          243° C.                                        Ex. 1 N.sub.2 (PEC)                                                                        205          224° C.                                        Ex. 2 Air (PEC)                                                                            210          248                                                   Ex. 2 N.sub.2 (PEC)                                                                        205          234                                                   Ex. 3 Air (PPC)                                                                            218          230                                                   Ex. 3 N.sub.2 (PPC)                                                                        215          225                                                   ______________________________________                                    

The above results show that in each case where an oxygen-phosphorus bond was formed and the active hydrogen atom replaced, the decomposition temperature of the polycarbonate increased substantially both in air and in nitrogen. The results also show that the different hydroxyl end capping agents in themselves had little influence on the decomposition temperature. Once the oxygen-phosphorus bond was formed. The decomposition temperature was increased by about the same amount. 

We claim:
 1. A process for improving the thermal stability of a normally solid polycarbonate having substantially alternating epoxide and carbon dioxide units and having a plurality of free hydroxyl groups represented by the formula: ##STR3## wherein: R₁ is hydrogen, a halomethyl group, or a hydrocarbyl group having from 1 to 6 carbon atoms;R₃ is hydrogen, a halomethyl group, or a hydrocarbyl group having from 1 to 6 carbon atoms; R₂ and R₄ are hydrogen or a hydrocarbyl group having from 1 to 6 carbon atoms; or R₁, r₂, r₃ and R₄ are combined together constituting a carbocyclic ring of from 4 to 7 carbon atoms; which comprises end-capping at least a portion of the free hydroxyl groups of said polycarbonate by reacting said hydroxyl groups with a hydroxyl reactive phosphorus compound having the ability to replace the active hydrogen atom on said hydroxyl group for forming an oxygen-phosphorus bond, said reaction being carried out under conditions sufficient for effecting said reaction.
 2. The process of claim 1 wherein R₂ and R₄ are hydrogen atoms.
 3. The process of claim 2 wherein R₁ and R₃ are hydrogen, a lower alkyl group having from 1 to 2 carbon atoms, or a phenyl group.
 4. The process of claim 3 wherein said hydroxyl reactive phosphorus compound is selected from the group consisting of a halophosphine, halophosphonate, halophosphate and halophosphite.
 5. The process of claim 4 wherein R₃ is hydrogen atom, or a methyl group.
 6. The process of claim 5 wherein R₁ is hydrogen, or a phenyl group.
 7. The process of claim 6 wherein R₁ and R₃ are hydrogen atoms.
 8. The process of claim 4 wherein said phosphorus compound is selected from the group consisting of chlorodiphenyl phosphine and chlorodiphenyl phosphate.
 9. An end-capped polycarbonate having improved thermal stability formed by reacting a normally solid polycarbonate having substantially alternating epoxide and carbon dioxide units and a plurality of free hydroxyl groups represented by the formula: ##STR4## wherein: R₁ is hydrogen, a halomethyl group, or a hydrocarbyl group having from 1 to 6 carbon atoms;R₃ is hydrogen, a halomethyl group, or a hydrocarbyl group having from 1 to 6 carbon atoms; R₂ and R₄ are hydrogen or a hydrocarbyl group having from 1 to 6 carbon atoms; or R₁, r₂, r₃ and R₄ are combined together constituting a carbocyclic ring of from 4 to 7 carbon atoms; with a hydroxyl reactive phosphorus compound whereby the active hydrogen atom on the hydroxyl group is replaced and an oxygen-phosphorus bond formed.
 10. The polycarbonate of claim 9 wherein R₂ and R₄ are hydrogen atoms.
 11. The composition of claim 10 wherein R₁ is selected from the group consisting of hydrogen and phenyl.
 12. The polycarbonate of claim 11 wherein R₃ is selected from the group consisting of hydrogen and methyl groups.
 13. The polycarbonate of claim 12 wherein n is from about 500 to 1,500. 